AU2011260345B2

AU2011260345B2 - Process and plant for lowering the residual carbon content of ash

Info

Publication number: AU2011260345B2
Application number: AU2011260345A
Authority: AU
Inventors: Nikola Anastasijevic; Gunter Schneider
Original assignee: Outotec Oyj
Current assignee: Metso Corp
Priority date: 2010-06-01
Filing date: 2011-05-30
Publication date: 2014-03-13
Anticipated expiration: 2031-05-30
Also published as: AU2011260345A1; BR112012030456A2; CN102917785A; EA025146B1; WO2011151294A1; US8876969B2; CN102917785B; EP2576043A1; EA201291250A1; CA2799063C; DE102010022400B4; DE102010022400A1; EP2576043B1; CA2799063A1; US20130068138A1; PL2576043T3

Abstract

This invention relates to lowering the carbon content in ash, wherein the ash is introduced into a reactor with a carbon content of 1 to 20 wt-% and is burnt there at temperatures of 700 to 1 100°C. During the combustion, microwave radiation is fed into the reactor and the energy released during the combustion is at least partly recovered.

Description

WO 2011/151294 PCT/EP2011/058856 Process and Plant for Lowering the Residual Carbon Content of Ash This invention relates to a process and a plant for lowering the residual carbon content 5 in ash, preferably in coal ash, in which ash with a carbon content of 1 to 20 wt-% is introduced into a reactor, in particular a fluidized-bed reactor, and is burnt at tempera tures of 700 to 1100 C, preferably 750 to 9000C. The residues of organic material produced during combustions are referred to as ash. 10 The composition of ash particles greatly depends on the combustible material and extends from residual carbon and minerals (quartz) over metallic compounds (mostly oxides and (bi-) carbonates, such as A1 2 0 3 , CaO, Fe 2 0 3 , MgO, MnO, P 2 0 5 , K 2 0, SiO 2 , Na 2

CO

3 , NaHCO3) up to toxic substances, such as heavy metals (e.g. arsenic and zinc) and dioxins. The residual carbon contained in the ash with an amount of up to 20 wt-% 15 for the most part is centered in a coal core, which is surrounded by metal oxide com pounds. Such ashes are not suitable for simple dumping, but must be declared as hazardous waste, since they are hygroscopic and with improper dumping the soluble components leached out thus can get into the groundwater. This form of ash is not usable either as filler in the cement industry, because the residual carbon content 20 deteriorates the binding properties. The problem of the residual carbon content in ash, in particular that of the fly ash ob tained in coal-fired power plants with a bulk density of 0.9 to 1.1 kg/I, is known just as experiments to penetrate the metal oxides protectively enveloping the carbon core with 25 microwave radiation. EP 0 521 059 B1 for example describes a method for determining the carbon content in fly ash. For this purpose, an ash sample is collected in a measur ing chamber which acts as microwave resonance space, and the sample is exposed to a microwave radiation. By measurements of the absorption of sample and reference materials, the dielectric constant of the sample material can be determined and thus 30 ultimately be used to estimate the residual carbon content. US 4,705,409 likewise describes the use of microwave radiation in conjunction with the determination of the carbon content in fly ash. For this purpose, the fly ash is exposed WO 2011/151294 PCT/EP2011/058856 -2 to a microwave radiation for absorbance measurement. Part of microwave radiation is absorbed hereby by carbon, the rest of the radiation is absorbed in an absorption fluid. From the difference of the temperature of this absorption fluid in measurements with and without ash sample the carbon content can be inferred. Due to the absorption of 5 the microwave radiation, a partial reduction of the carbon content in the fly ash can occur, which requires, however, a comparatively high radiation energy. A process for the thermal treatment of granular solids, in particular for roasting ores, in a reactor with fluidized bed in which microwave radiation from a microwave source is 10 fed into the reactor, is known for example from DE 102 60 745 Al. To improve the utilization of energy and the feeding of the microwave radiation, a gas or gas mixture is introduced into a mixing chamber of the reactor from below through a central supply tube, wherein the gas supply tube is at least partly surrounded by a stationary annular fluidized bed fluidized by supplying fluidizing gas. The feeding of the microwaves is 15 effected through the central gas supply tube. It is the object of the present invention to completely combust in an efficient way the residual carbon of the ash and at the same time provide a procedure which is as efficient as possible in energetic terms. 20 This object is solved by the invention with the features of claim 1, in that the ash with a carbon content of 1 to 20 wt-% is introduced into a reactor and burnt there at tempera tures of 700 to 1100 C, preferably 750 to 9000C, wherein during the combustion micro wave radiation is fed into the reactor and the energy released during the combustion is 25 at least partly recovered. Here, the use of a fluidized-bed reactor is advantageous above all, as in this way a particularly high amount of the ash surface can be reached by the microwave radiation per unit time. Due to the irradiation with microwaves, the residual carbon in the ash can be preferably heated which results in a improved com bustion rate.. The energy released by combustion of the residual carbon is partly re 30 covered later. . The combustion temperature is maintained at -800 0C by feeding in the corresponding amount of air or additional fuel. Under adiabatic conditions the tempera ture increase AT can be expressed as a non-linear function to the residual carbon content, according to which with 1 wt-% of carbon in the fly ash the temperature in- WO 2011/151294 PCT/EP2011/058856 -3 crease per weight percent of carbon is -290 0C, with 5 wt-% of carbon the temperature increase per weight percent of carbon is ~170 C, and with 10 wt-% of carbon the temperature increase per weight percent of carbon is -120 0C (assumptions: SiO2 major mineral component of ash and oxygen content of the off-gas in the range of 1.7 5 to 1.8%). Thus, the ash can not only be converted to a material suitable for dumping or even usable in the cement industry, but the carbon content can also be utilized for recovering energy. After the combustion, the residual carbon content of the remaining ash residues is 10 below 0.1 wt-%, preferably not more than 0.01 wt-%. In a preferred aspect of the invention, the ash is charged into the reactor with a tem perature of at least 1000C, preferably at least 1200C, particularly preferably 1500C to 3000C, as in this way less additional energy must be supplied for the combustion 15 process. In particular, it was found to be favorable that directly after its production, e.g. in a coal-fired power plant, the ash is subjected to the process of the invention. That would allow a direct processing of preheated dry ash. Otherwise, the ash which above all after being dumped temporarily can have a residual 20 water content of up to 20 wt-%, in particular of up to 15 wt-%, can be supplied to a drying means provided upstream of the reactor. In this drying means, the ash is pre heated to a temperature of at least 1000C, preferably at least 1200C, particularly pre ferably 1500C to 3000C, wherein at the same time water contained in the ash is evapo rated due to such heating. Due to such pretreatment it is possible to reduce the amount 25 of energy to be introduced into the reactor. In a preferred embodiment of the invention, the water obtained during drying is supplied to a steam generator as condensate and at least parts of this steam are again recircu lated into the drying means as energy carrier. Due to this cycle inside the drying stage 30 energy losses can be minimized. One aspect of the energy recovery in accordance with the invention provides that the energy released in the reactor is at least partly utilized for steam generation. When the WO 2011/151294 PCT/EP2011/058856 -4 process includes a drying means, it is recommendable in particular to at least partly use the energy released during the combustion for evaporating the condensate ob tained during drying in the steam generator and to again supply the steam thus ob tained to the drying means. Downstream of the steam generation further units can be 5 provided for energy recovery. Furthermore, the introduction of additional fuel, in particular coal, into the reactor is possible in accordance with the invention. As a result, the combustion temperature can be kept constant in the particularly favorable range of 750 to 9000C. In addition, it is not 10 necessary that the entire input of energy is effected by the microwave radiation. The use of coal as fuel is recommendable in particular when the process of the invention is performed downstream of a coal-fired power plant and coal thus is easily available. To optimize the mass and heat transfer, it is favorable to introduce a gas or a gas 15 mixture from below through a preferably central gas supply tube (central tube or central tuybre) into a mixing chamber of the reactor, wherein the gas supply tube is at least partly surrounded by a stationary annular fluidized bed of the ash which is fluidized by supplying fluidizing gas, and the microwave radiation is guided through the same gas supply tube into the mixing chamber. The gas introduced through the gas supply tube 20 and/or the fluidizing gas contains the oxygen required for the combustion. A plant in accordance with the invention, which is suitable in particular for performing the process described above, includes a reactor formed as fluidized-bed reactor for the heat treatment of the ash, and a microwave source. To the reactor a gas supply system 25 furthermore is connected, which is formed such that the gas flowing through the gas supply system entrains solids from the stationary annular fluidized bed of the ash into a mixing chamber of the reactor, wherein the microwave radiation generated by the microwave source can be fed in through the gas supply system. At the same time, a fuel conduit for introducing fuel opens into the reactor. Finally, the plant also includes a 30 unit for heat recovery provided downstream of the reactor. An improvement of the plant is obtained when upstream of the reactor a drying means is provided, which is operated in a cycle with steam from a steam generator. In this WO 2011/151294 PCT/EP2011/058856 -5 cycle, the condensate obtained in the drying means is introduced through a conduit into the steam generator, where by feeding in energy, preferably that energy which is ob tained during the combustion in the reactor, it is converted into steam and as such passed back into the drying means. 5 Further developments, advantages and possible applications of the invention can also be taken from the following description of embodiments and the drawing. All features described and/or illustrated form the subject-matter of the invention per se or in any combination, independent of their inclusion in the claims or their back-reference. 10 In the drawing: Figure 1 shows a process diagram of a process and a plant in accordance with a first embodiment of the present invention; 15 Figure 2 shows a process diagram of a process and a plant in accordance with a second embodiment of the present invention; Figure 3 schematically shows the configuration of a plant in accordance with the 20 invention. Figure 1 shows a process without predrying stage in accordance with a first embodi ment of the invention. Via a conduit 1, dry ash with a temperature of e.g. 2500C and a mass flow of e.g. 10 t/h is supplied to a combustion reactor 3. At the same time, coal is 25 introduced into the reactor 3 via a conduit 2 as further fuel with ambient temperature (e.g. 250C). In principle, other fuels can also be used here, such as Diesel, gasoline or gas. Via a microwave source 4, the reactor 3 is charged with electromagnetic waves (mi 30 crowaves), wherein different wavelengths can be set. Suitable microwave sources include e.g. a magnetron or a klystron. Furthermore, high-frequency generators with corresponding coils or power transistors can be used. The frequencies of the electro magnetic waves emitted by the microwave source usually lie in the range from 300 WO 2011/151294 PCT/EP2011/058856 -6 MHz to 30 GHz. Preferably, the ISM frequencies 435 MHz, 915 MHz and 2.45 GHz are used. The combustion in the reactor 3 is effected at 700 to 11 000C, preferably 750 to 900'C. 5 As oxygen source, the air compressed in a compressor 6 is injected into the reactor 3 via conduits 5 and 7. If the reactor constitutes a fluidized-bed reactor, the gas contain ing oxygen can be used as fluidizing gas and/or be fed in separately. The utilization of air as oxygen carrier is particularly favorable, as it can be withdrawn from the surround ing atmosphere without additional costs. In principle, however, pure oxygen can be 10 used just as any gas mixture containing oxygen. Compression is not absolutely neces sary either. Via conduit 8, the hot combustion residues and gases of e.g. 800'C are delivered into an energy recovery 9. This energy recovery 9 can be e.g. a unit for steam generation, 15 wherein the steam then is utilized for generating electric energy by means of a steam turbine. If the plant of the invention is provided downstream of a power plant, this steam can also be admixed to the steam flow obtained in actual operation of the power plant. From the energy recovery 9 the combustion residues and waste gases with a tempera 20 ture of e.g. 2500C are transferred via a conduit 10 into a cyclone 11, in which ash is separated from waste gases. For separating the solids from the waste gases, however, other separating means such as a filter are also possible. The residual ash is withdrawn from the process via conduit 12, while the waste gases are discharged from the cyclone via conduit 13. 25 Figure 2 shows the process of the invention and the associated plant with an upstream means for drying the ash. For this purpose, the ash with a residual water content of 15% is charged into a drier 21 via conduit 1. Via a conduit 22, the condensate obtained in the drier 21 is supplied to a steam generator 23, from which it can again be supplied 30 as energy carrier to the drying stage 21 via conduit 24. Waste gases from the drying stage 21 are discharged via conduit 25. Via conduit 20, the dried ash then is supplied to the combustion reactor 3 with a temperature of e.g. 110 0C and a mass flow of e.g. 10 t/h.

WO 2011/151294 PCT/EP2011/058856 -7 Via conduit 2, coal with an ambient temperature of 25'C at the same time is introduced into the reactor 3 as further fuel. Here as well, air with a temperature of e.g. 250C serves as oxygen source. Via the microwave source 4, microwave radiation additionally 5 is introduced into the reactor 3, in order to activate the carbon core of the ash and make it accessible to the combustion. Due to the combustion in accordance with the invention, the residual carbon content of the ash can be lowered down to 0.1 wt-% or even 0.01 wt-% in this embodiment as also in the first embodiment. 10 The hot residues and waste gases with a temperature of about 800'C are supplied via conduit 8 to the steam generator 23, in which the condensate from the drying stage 21 is converted into steam. With an excess amount, further steam can be withdrawn from the steam generator 23 for energy utilization. As a result, it often is required to intro duce additional water either into the steam generation itself or into the supply conduit 15 22 via a non-illustrated conduit. In principle, it is also possible to utilize only a part of the energy generated by the combustion in the steam generator 23 and provide at least one further downstream, non-illustrated energy generation stage. After the last energy generation stage, which in Figure 2 is the steam generation 23, 20 the gas/solids mixture is delivered into the cyclone 11 for separation, where the ash now almost liberated from carbon is separated from the hot waste gases with a tem perature of still e.g. 2500C. Figure 3 shows the configuration of a plant of the invention with the claimed design of 25 the reactor 3, into whose e.g. cylindrical body a central tube 35 opens such that it extends substantially vertically upwards from the bottom of the reactor 3. In the region of the bottom of the reactor 3 a non-illustrated gas distributor is provided, into which a supply conduit 32 for fluidizing gas opens. In the vertically upper region of the reactor 3, which forms a mixing chamber 34, an outlet 36 is arranged, which via conduit 8 opens 30 into the unit for energy recovery 9. From this unit 9, both the waste gas and the par ticles contained therein are transferred via conduit 10 into the non-illustrated separating means 11. At the end of the central tube 35 opposite to the reactor 3 a microwave WO 2011/151294 PCT/EP2011/058856 -8 source 4 is arranged. The microwave rays produced there are introduced into the mixing chamber 34 via the central tube 35. Via the solids conduit 1 the ash is introduced into the reactor 3 and forms a layer 33 5 annularly surrounding the central tube 35 above the bottom of the reactor 3. This annu lar fluidized bed 33 is fluidized by the gas introduced via conduit 32 such that a statio nary fluidized bed is formed. The velocity of the gases supplied to the reactor 3 prefer ably is adjusted such that the Particle Froude Number in the annular fluidized bed 33 lies between about 0.115 and 1.15. The Particle Froude Number is defined as: 10 (P~f*d,*g P0f with 15 u = effective velocity of the gas flow in m/s ps = density of the solid particles in kg/m 3 pf = effective density of the fluidizing gas in kg/m 3 d= mean diameter in m of the particles of the reactor inventory present during opera tion of the reactor (or of the particles formed) 20 g = gravitational constant in m/s 2 . The height level of the annular fluidized bed is adjusted such that solids get over the edge of the central tube 35 and thus are entrained into the mixing chamber 34 by the gas flowing through the central tube 35. The velocity of the gas supplied to the reactor 25 3 through the central tube 35 preferably is adjusted such that the Particle Froude Num ber in the central tube 35 lies between about 1.15 and 20 and in the mixing chamber 7 between about 0.37 and 3.7. Via conduit 2, further fuel is also introduced into the reactor 3. In the case of liquid or 30 gaseous fuel, the same preferably is injected such that a uniform distribution is ob tained over the entire mixing chamber 34. If the fuel is present in solid form, the solids WO 2011/151294 PCT/EP2011/058856 -9 become part of the annular fluidized bed 33, which is why fuel and ash must be intro duced into the reactor 3 in the desired quantity ratio for adjusting the required solids level of the annular fluidized bed chamber 33. 5 Example 1 The following Table 1 represents the mass flows obtained by simulation as well as energy inputs and outputs of a process as it is shown in Figure 1. 10 Table 1 C of V Micro- Recovered 02 dry V (air) (waste M (coal) waves M (ash) energy (waste ash gas) gas) wt-% Nm 3 /h Nm 3 /h t/h MW t/h MW mol-% 1.0 2694 2906 0.40 0.139 10.0 2.4 3.0 2.0 2666 2794 0.24 0.142 9.9 2.3 3.0 3.0 2638 2681 0.08 0.144 9.8 2.3 3.0 4.0 4275 4275 0.00 0.166 9.7 2.6 7.7 5.0 7558 7558 0.00 0.207 9.6 3.3 11.0 6.0 10841 10841 0.00 0.249 9.5 4.0 12.2 7.0 14125 14125 0.00 0.290 9.4 4.8 12.9 8.0 17408 17408 0.00 0.332 9.3 5.5 13.4 9.0 20691 20691 0.00 0.373 9.2 6.2 13.6 10.0 23974 23974 0.00 0.415 9.1 6.9 13.9 The process simulation underlying Table 1 proceeds from a mass flow of the ash of 10 t/h at a temperature of 2500C. Air and coal both have a temperature of 250C. The exit 15 temperature from the reactor is 800'C, the final waste gas temperature is 2500C. Table 1 correlates the carbon content of the dry ash (column 1) with the volume flow of the air injected into the reactor (column 2), the volume of the resulting waste gas (col umn 3), the used mass flow of the additional fuel coal (column 4), the microwave ener 20 gy fed into the reactor 3 (column 5), the used mass flow of the dry ash (column 6), the WO 2011/151294 PCT/EP2011/058856 - 10 energy obtained in the energy recovery (column 7), and the residual oxygen content in the waste gas (column 8). The amount of converted air increases just like the resulting waste gases with the 5 increase of the carbon content in the ash. From a carbon content of 4 wt-% the carbon content of the ash is so high that no further fuel must be supplied in the form of coal. The used microwave radiation hardly plays a role for the required amount of additional fuel. 10 It is found that due to the invention a considerable amount of energy becomes usable, which previously was lost unused along with the ash. Example 2 15 Example 2 refers to the simulation of a process as it is shown in Figure 2. In Example 2, the simulation is based on a mass flow of the ash of 10 t/h at a temperature of 25'C before drying (after drying 110 C) and a water content of 15 wt-%. The ash has a residual carbon content of 15 to 25 wt-%. Air and coal both have a temperature of 250C. The exit temperature from the reactor is 8000C, the final waste gas temperature 20 is 250'C. Table 2 represents the carbon content of the dry ash (column 1) with the volume flow of the air injected into the reactor (column 2), the volume of the resulting waste gas (col umn 3), the used mass flow of the additional fuel coal (column 4), the microwave ener 25 gy fed into the reactor 3 (column 5), the used mass flow of the dry ash (column 6), the energy obtained in the energy recovery (column 7), and the residual oxygen content in the waste gas (column 8) in a process with integrated predrying of the ash: 30 - 11 Table 2 C of V Micro- Recovered 02 dry V (air) (waste M (coal) waves M (ash) energy (waste ash gas) gas) wt-% Nm 3 /h Nm 3 /h t/h MW t/h MW mol-% 1.0 3287 3546 0.49 0.161 10.0 1.0 3.0 2.0 3261 3435 0.33 0.163 9.9 1.0 3.0 3.0 3234 3323 0.17 0.165 9.8 1.0 3.0 4.0 3208 3212 0.01 0.168 9.7 0.9 3.0 5.0 6321 6321 0.00 0.207 9.6 1.6 9.0 6.0 9603 9603 0.00 0.249 9.5 2.3 11.1 7.0 12883 12883 0.00 0.290 9.4 3.0 12.2 8.0 16163 16163 0.00 0.332 9.3 3.7 12.8 9.0 19444 19444 0.00 0.373 9.2 4.5 13.2 10.0 22725 22725 0.00 0.415 9.1 5.2 13.5 5 Table 2 confirms the results shown in Example 1, but in absolute terms the energy recovered is lower than in Example 1, since parts of the energy are used for evaporating the condensate in the drying stage. Due to the higher energy demand with a simultaneously lower inlet temperature of the ash (Example 1: 250 0 C, Example 2: 110*C) it is only from a carbon content of at least 5 wt-% that no further 10 fuel must be supplied in the form of coal. It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country. 48821651 (GHMatters) P91817.AU WO 2011/151294 PCT/EP2011/058856 - 12 List of Reference Numerals 1 conduit 2 conduit 5 3 reactor 4 microwave source 5 conduit 6 compressor 7 conduit 10 8 conduit 9 unit for energy recovery 10 conduit 11 cyclone 12 conduit 15 13 conduit 20 conduit 21 predrying 22 conduit 23 steam generator 20 24 conduit 25 conduit 31 conduit 32 conduit 33 annular fluidized bed 25 34 mixing chamber 35 central tube 36 outlet

Claims

1. A process for lowering the carbon content in ash, in which ash with a carbon content of 1 to 20 wt-% is introduced into a reactor and burnt there at temperatures of 5 700 to 11000C, wherein during the combustion microwave radiation is fed into the reactor and the energy released during the combustion is at least partly recovered, characterized in that in addition fuel, including coal, is introduced into the reactor.

2. The process according to claim 1, characterized in that the residual carbon 10 content of the ash after the combustion is not more than 0.1 wt-%.

3. The process according to any of the preceding claims, characterized in that ash with a temperature of at least 1000C is introduced into the reactor. 15

4. The process according to any of the preceding claims, characterized in that ash with a residual water content of up to 20 wt-% is supplied to a drying means provided upstream of the reactor.

5. The process according to claim 4, characterized in that the water obtained 20 during drying is supplied to a steam generator as condensate and the steam obtained in the steam generator is at least partly again supplied to the drying means as energy carrier.

6. The process according to any of the preceding claims, characterized in that the 25 energy released in the reactor is at least partly utilized for steam generation.

7. The process according to any of the preceding claims, characterized in that a gas or a gas mixture is introduced into a mixing chamber of the reactor from below through at least one gas supply tube, wherein the gas supply tube is at least partly 30 surrounded by a stationary annular fluidized bed consisting of ash which is fluidized by supplying fluidizing gas, and that the microwave radiation is supplied to the mixing chamber through the gas supply tube.

8. A plant for lowering the carbon content in ash with a reactor with fluidized bed, 35 wherein the reactor includes a gas supply system which is formed such that gas 48821651 (GHMatters) P91817.AU - 14 flowing through the gas supply system entrains ash from a stationary annular fluidized bed, which at least partly surrounds the gas supply system, into a mixing chamber, with a solids conduit for feeding ash into the reactor, with a microwave source for feeding microwave radiation into the reactor through the gas supply system, with a fuel 5 conduit for feeding fuel into the reactor, and with a unit for energy recovery provided downstream of the reactor.

9. The plant according to claim 8, characterized in that upstream of the reactor a drying means is provided, which is operated in a cycle with steam from a steam 1o generator.

10. A process for lowering the carbon content in ash substantially as herein described with reference to the accompanying figures. 15

11. A plant for lowering the carbon content in ash with a reactor with fluidized bed substantially as herein described with reference to the accompanying figures. 48821651 (GHMatters) P91817.AU